Process for preparing aliphatic fluorine compounds



United States Patent PRDGESS FOR PREPARING ALIPHATIC' ELUORINE Claims priority, application Germany Apr. 4, 1952 12' Claims. (Cl. 260-96533) invention relates to a process for preparing aliphatic fluorine compounds and more particularly to such a process in whichaluminumfluorideis used as a catalyst.

This application is a, division of application Serial No. 699,890, filed December 2, 1957, now abandoned.

It is known that aliphatic fluorine compounds can be prepared by passing hydrogen fluoride and chlorinated hydrocarbons simultaneously over. solid metal halides such. as the chlorides of copper, silver, gold, zinc cadmiummercury, vanadium, manganese, iron, cobalt, nickel, or. platinum, which metal halides act. as catalysts. The. catalysts may also be precipitatedon carriers in order to.- form. a large catalytically active surface.

In U.S.. patentappl. Ser. No. 344,456 filed. March 24, 1953., nowabandoned; of which. this application is a continuationrinrpart, we disclosed that especially good yields of. highly fluorinated compounds'are obtained by-using aluminum fluoride as a catalyst at a temperature within the range of 300 C. tofZQO C., and especially from 300 to 500 C. Now we have furthermore found that good yields of fluorinated compounds are not only .obtained, the above reaction is carried out at temperatimes from 300 to 700 6., but also at a temperature in therange from 200 to 300 C., advantageously above 230 C1, in other Words, according-to the invention vaporous saturated halogenated aliphatic hydrocarbons containing one or more halogen atoms (other than fluorine) and which may additionally contain one or more fluorine atoms, are reacted with hydrogen fluoride vapor in the presence of analuminum fluoride: catalyst at a temperature in the range from- 200 to 700 C., advantageously from 2 3010 500" C; Surprisingly there is obtained a. good yield ot fluorinated compounds, notronly if the reaction is carried out at a temperature above 3'00? C.,, but also, inv the. above mentioned range ofrtemperature below: 300 C. The process of the invention. is especially advantageous when carbon tetrachloride. isused as starting material. However, there may likewise be used other halogenated aliphatic hydrocarbons which are the'formof vapor under the reaction conditions. It is ofi'advantage to-carr-y out the. process at aslowtemperatures as possible, since then the catalyst has a longer lifetime and, therefore, it has to be exchanged less often; Consequently the apparatus can better be utilized. Furthermorethe material of: the apparatus has a longer lifetime.

These highly fluorinated compounds have. many uses among; which; most notably is their use as refrigerants.

An. especially active aluminum fluoride catalyst is: obtained bytreating. metallic aluminum in a; form. having a large surface, for instance, in the form of chips or filings, with. hydrogen fluoride at a raised temperature. Catalysts having the same good activity canbe obtained by heating; in a. current of. hydrogen fluoride activated alumina, advantageously in the. form: of pieces,. such. as

Patented July 26, 1960 is used for the dehydration of ethanol. Crystalline fused alumina cannot be used as no substantial amount of aluminum fluoride is formed so that practically no catalytic action. occurs. v

The reaction components are mixed" together in the form of their vapors. in the desired proportions and introduced into the reaction chamber, which is filled with a the catalyst. The reaction vessel may be, for example, a

tube made of. nickel or steel coated with nickel or any other material which is resistant to hydrogen fluoride at high temperatures. 7

In general the reaction may be conducted. under atmospheric pressure, and in this case the construction of the apparatus and the means. for sealing it and supplying it with the reactants are simplified. 7

The mixture leaving the reaction. vessel is freed from acid constituents by washing it with water and a solution of an alkali hydroxide. The reaction products are condensed and separatcdfromone another by fractionation..

v The temperature required for the lluorination lies within the range of 200m 700' C. Thehigher the temperature the more highly fluorinated are the" products' formed. The hydrogen fluoride is consumedalmost quantitatively, especially if the quantity thereof is kept somewhat below the stoichiometrically calculated amount.

Whereas the use of aluminum fluoride alone generally leads to the production of mixtures of the various possible fluorination products, the relative proportions of thereaction products can be controlled by adding other metal halides to the aluminum fluoride. Thus, the formationof ,trifluoro-chloro-methane from carbon tetrachloride and hydrogen fluoride can be avoided almost completely by addinga small quantity. of magnesium fluoride to the catalyst. If, on .the' other hand, the formation of trifluoro-chloromethane is to be promoted, the addition of a copper halide has been found suitable. The sameresult is obtained. by mixingl'tlre almninum catalyst with copper chips: or filings. It is: smiprising that, inspite'ot: the: addition: oi copper, which. usually promotes the formation ofv highly fluorin'ated compounds, no tetrafluoromethane isformed, whereas without addition of copper large: quantities of this compoundl are obtained under'otherwi'se identical conditions Consequently it is possible by suitably selecting the: catalysts to promote the formation of certain fiuorination products the formation of which could: not be promoted to thesame extent by adjusting: the stoichiometric proportions: ofi't'h' reactants or by regulating the temperature. A special advantage of the process'of. the-present invention is that it. is possible to prevent or diminish the formationv of undesirable compounds which: cannot. be reused as. startingmaterials. 7

The aforesaid mixed catalysts canbe prepared invan ious ways. Thus, alloys may be used which containthe desired metals ascomponents of the alloy, for example, an alloy of aluminum and copper, or piecesof alumina may be. impregnated with asolution of salts of the appropriate metals. in all. cases the mixed catalysts should bepre-treatedwithhydrogen fluoride. c 1

For the manufacture of. fluorinated ethane derivative itisof advantage in some cases to use as starting, matcrials instead of ethane derivatives ethylene compounds and chlorine to form. the corresponding: ethane derivatives which. are then reacted in statu nescendi to yield the desired fluorine containing compounds. For example; trifluoro-trichlor-ethane may be prepared from tetrachlorethylene by reacting it. simultaneously with chlorine 3 Example 1 250 grams of hydrogen fluoride vapor are passed in .the course of hours at a gradually increasing temperature through a nickel tube having an internal diameter of 5 cm. filled with aluminum turnings and built into an electric oven. Over the catalyst so pretreated there is passed at 300380 C. (measured at the external Wall of the nickel tube) in the course of 18 /2 hours a mix- 'ture of 1135 grams of hydrogen fluoride and 5115 grams of carbon tetrachloride in the form of their vapors. The vapors leaving the reaction tube are washed with water and sodium hydroxide solution, dried with concentrated sulphuric acid, and condensed and fractionated by distillation. The reaction product consists of 56.6 percent of difluoro-dichloromethane, 8.7 percent of trifluoro-chloromethane, 16.8 percent of monofluoro-trichloromethane and 17.9 percent of unreacted carbon tetrachloride. The extent of conversion of the carbon tetrachloride amounts to 86 percent and that of hydrogen fluoride to 96 percent.

Example 2 A nickel tube having an internal diameter of 2.5 cm. and of which a length of 30 cm. is situated in an electrically heated oven, is filled with pieces of activated alumina and heated to 360-400 C. The temperature is measured at the external wall of the reaction tube. Hydrogen fluoride is passed through the tube for about 40 hours. A mixture of the vapors of carbon tetrachloride and hydrogen fluoride in the molecular ratio of 1:19 is passed through the tube at the rate of 1 gram molecule of carbon tetrachloride per hour, and a reaction product is obtained which consists of 18 percent of monofluordtrichloromethane, 43 percent of difluoro-dichloromethane and 19 percent of trifluoro-m0nochloromethane. 19.5 percent of the carbon tetrachloride used are recovered. The hydrogen fluoride is almost completely consumed.

Example 3 A catalyst of alumina impregnated with a magnesium chloride solution of 60 percent strength (calculated as MgCl .6H O) is fluorinated as described in Example 2. By passing the mixture of carbon tetrachloride and hydrogen fluoride used in Example 2 over this catalyst under the conditions described in that example, a mixture is obtained which consists of 29.4 percent of monofluoro-trichloromethane, 62.8 percent of difluoro-dichloromethane, 1.6 percent of trifluoro-monochloromethane and 6.1 percent of unreacted carbon tetrachloride. The hydrogen fluoride is completely consumed.

Example 4 319 grams of carbon tetrachloride vapor and 119 grams of hydrogen fluoride vapor are passed per hour at 450-500 C. over a mixture of pieces of activated alumina and copper turnings which has been pretreated with hydrogen fluoride for 32 hours while the temperature rose from 80 C. to 500 C. The yields of pure fluo'rine compounds calculated on the carbon tetrachloride used amount to 82 percent of trifluoro-chloromethane, percent of difluo'ro-dichloromethane and 3 percent of monofluoro-trichloromethane. 94 percent of the hydrogen fluoride are consumed. Without the addition of copper turnings there are obtained only 54 percent .of trifluoro-chloromethane in addition to 17 percent of difluoro-dichloromethane, 12 percent of monofiuoro-trichloromethane and about 7 percent of tetrafluoromethane.

Example 5 With the aid of the catalyst described in Example 5 a mixture of 4.07 gram molecules of difluo'ro-dichloromethane per hour and 4.00 gram molecules of hydrogen fluoride per hour is converted into trifluoro-chlororneth- 4 ane in a yield of 79.5 percent. No tetrafluoromethane is formed.

Example 6 A mixture of 1 gram molecule of tetrachlorethylene, 1 gram molecule of chlorine and 3 gram molecules of hydrogen fluoride is passed, per hour, at 400-450 C. over a catalyst as described in Example 2. 1:1:2-trifluoro-lz2z2-trichlorethane is obtained in good yield in addition to a small amount of 1:2-difluoro-tetrachlorethane and unreacted tetrachlorethylene.

Example 7 Lumpy, porous alumina is treated at 150-300" C. with gaseous hydrogen fluoride (2.5 kg.) in a nickel tube (diameter: 5 cm.; length: 1 m.) in an electrically heated tube furnace. A mixture prepared from 1 mol of chloroform and 3 mols of hydrogen fluoride is passed over the catalyst at 450-480 C. at a rate of 1 mol of chloroform per hour. The yield obtained, calculated upon the chloroform used, is of trifluoromethane, 2.6% of difluoromethane and 6.3% of monofluorodichloromethane. 90% of the hydrogen fluoride is consumed.

Example 8 A nickel tube having an internal diameter of 2.5 cm. and of which a length of 35 cm. is situated in an electrically heated oven, is filled with pieces of porous alumina' impregnated with a solution of 60% strength of magnesium chloride. It is heated to 250 C. (the temperature is measured at the external wall of the nickel tube), and a current of gaseous hydrogen fluoride is passed through the tube for 20 hours at 200-250 C. Then a gaseous mixture of 1 mol/ h of carbon tetrachloride and 1.86 mols/h of hydrogen fluoride is passed through at 230-250 C. The composition of the reaction product so obtained is as follows:

1.45 percent by weight of trifluoro-monochloromethane 81.2 percent by weight of difluoro-dichloromethane 12.5 percent by weight of monofluoro-trichloromethane 4.25 percent by weight of carbon tetrachloride 99.40 percent by weight.

We claim:

1. A process for the manufacture of saturated aliphatic fluorine compounds by replacing halogen by fluorine, which process comprises reacting hydrogen fluoride, at a temperature Within the range of about 200 C. to 700 C. and in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst, with saturated halogenated aliphatic hydrocarbons containing at least one halogen atom other than fluorine.

2. A process for the manufacture of saturated aliphatic fluorine compounds by replacing halogen by fluorine, which process comprises reacting hydrogen fluoride, at a temperature Within the range of about 300 C. to 700 C. and in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst, with saturated halogenated aliphatic hydrocarbons containing at least one halogen atom other than fluorine.

in addition magnesium fluoride, as a catalyst, with saturat ed halogenated aliphatic hydrocarbons containing at least one halogen atom but free from fluorine.

4. A process for the manufacture of saturated aliphatic fluorine compounds by replacing halogen by fluorine, which process comprises reacting hydrogen fluoride, at a temperature within the range of about 300 C. to 500 C. and in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst, with saturated halogenated aliphatic hydrocarbons containing at least one halogen atom but free from fluorine.

5. A process for the manufacture of saturated aliphatic fluorine containing compounds which comprises reacting at a temperature Within the range of about 300 to 500 C. a halogenated ethylene which contains at least one halogen atom different from fluorine with chlorine and hydrogen fluoride in the presence of aluminum fluoride containing in addition magnesium fluoride as catalyst, whereby the chlorine adds to the ethylene to form a saturated ethane, the hydrogen fluoride then reacting with the ethane to introduce a fluoride atom in place of one of said halogen atoms different from fluorine.

6. A process for the manufacture of saturated aliphatic fluorine compounds by replacing halogen by fluorine which process comprises reacting tetrachloro ethylene with chlorine and hydrogen fluoride at a temperature within the range of about 300 to 500 C. in the presence of aluminum fluoride containing in addition magnesium fluoride, whereby the chlorine adds to the tetrachloro ethylene to form hexachloro ethane, the hydrogen fluoride then reacting with the hexachloro ethane to introduce at least one fluorine atom in place of chlorine.

7. A process for the manufacture of difluorodichloromethane which comprises reacting hydrogen fluoride and carbon tetrachloride at a temperature in the range from about 200 to 700 C. in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst.

8. A process for the manufacture of difluorodichloromethane which comprises reacting hydrogen fluoride and carbon tetrachloride at a temperature in the range from about 300 to 700 C. in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst.

9. A process for the manufacture of difluorodichloromethane which comprises reacting hydrogen fluoride and a carbon tetrahalide which contains at least 2 chlorine atoms and at least one further halogen atom other than fluorine at a temperature in the range from about 300 C. to 700 C. in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst.

10. A process for the manufacture of saturated aliphatic fluorine compounds for replacing halogen by fluorine, which process comprises reacting hydrogen fluoride, at a temperature within the range of about 300 C. to 700 C. and in the presence of aluminum fluoride containing in addition magnesium fluoride and having been obtained by passing hydrogen fluoride over small pieces of an alloy aluminum and magnesium at a raised temperature, as a catalyst, with saturated halogenated aliphatic hydrocarbons containing at. least one halogen atom but free from fluorine.

11. A process for the manufacture of saturated aliphatic fluorine compounds for replacing halogen by fluorine, which process comprises reacting hydrogen fluoride, at a temperature within the range of about 300 C. to- 700 C. and in the presence of aluminum fluoride containing in addition magnesium fluoride and having been obtained by passing hydrogen fluoride at a raised temperature over pieces of porous alumina, impregnated with a magnesium salt, at a raised temperature, as a catalyst, With saturated halogenated aliphatic hydrocarbons containing at least one halogen atom but free from fluorine.

12. A process for the manufacture of saturated aliphatic fluorine compounds by replacing halogen by fluorine, which process comprises reacting hydrogen fluoride, at a temperature within the range of about 300 C. to 700 C. and in the presence of aluminum fluoride containing in addition magnesium fluoride as a catalyst, with saturated halogenated aliphatic hydrocarbons containing at most two carbon atoms and at least one halogen atom other than fluorine.

References Cited in the file of this patent UNITED STATES PATENTS 2,744,147 Milks May 1, 1956 2,744,148 Ruh et a1. May 1, 1956 2,748,177 Miller et a1. May 29, 1956 2,755,313 Calfee et al June 17, 1956 FOREIGN PATENTS 770,640 Great Britain Mar. 20, 1957 

